Method for Manufacturing All Solid-State Battery Comprising Polymeric Solid Electrolyte and All Solid-State Battery Obtained Thereby

ABSTRACT

The present disclosure relates to an all solid-state battery cell and a method for manufacturing the same. The gaps between the electrode active material particles forming the electrode active material layer are filled with a mixture of a polymeric solid electrolyte with a conductive material, and an organic solid electrolyte membrane is interposed between the positive electrode and the negative electrode. The method comprises a solvent annealing process to improve the contact between the electrode active material particles and the conductive material and to improve the contact between the electrode active material layer and the organic solid electrolyte membrane, thereby providing an all solid-state battery cell with improved ion conductivity and capacity realization.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a national phase entry under 35 U.S.C. § 371 of International Application No. PCT/KR2019/005377 filed May 3, 2019, which claims priority from Korean Patent Application No. 10-2018-0051476 filed May 3, 2018, all of which are incorporated herein by reference.

TECHNICAL FIELD

The present disclosure relates to a method for manufacturing an all solid-state battery comprising a polymeric solid electrolyte and an all solid-state battery obtained thereby.

BACKGROUND ART

A lithium ion battery using a liquid electrolyte has a structure in which a negative electrode and positive electrode are defined by a separator, and thus may cause a short-circuit when the separator is damaged by deformation or external impact, resulting in a risk, such as overheating or explosion. Therefore, it can be said that development of a solid electrolyte capable of ensuring safety is a very important problem in the field of lithium ion secondary batteries.

A lithium secondary battery using a solid electrolyte has enhanced safety, prevents leakage of an electrolyte to improve the reliability of a battery, and facilitates manufacture of a thin battery. In addition, lithium metal may be used as a negative electrode to improve energy density. Thus, such a lithium secondary battery using a solid electrolyte has been expected to be applied to a high-capacity secondary battery for electric vehicles in addition to a compact secondary battery, and has been spotlighted as a next-generation battery.

However, a lithium secondary battery using a solid electrolyte has lower ion conductivity as compared to a battery using a liquid electrolyte and particularly shows degradation of output characteristics at low temperature. In addition, such a solid electrolyte is problematic in that it shows lower surface adhesion to an active material, as compared to a liquid electrolyte, to cause an increase in interfacial resistance, and is distributed while not being in contact with an electrode active material to cause degradation of output characteristics or capacity characteristics as compared to the amount of a conductive material introduced to an electrode.

FIG. 1 is a schematic view illustrating an all solid-state battery which comprises an electrode for an all solid-state battery comprising a polymeric solid electrolyte according to the related art. FIG. 1 shows an all solid-state battery 100 which comprises: a current collector 111, 112; an electrode active material layer 140, 130 formed on one surface of the current collector; and a solid electrolyte membrane 120 interposed between the electrode active material layers. In addition, the electrode active material layer 130 may comprise a plurality of electrode active material particles 131, a polymeric solid electrolyte 133 and a conductive material 132. In the all solid-state battery, the electrode active material particles and the polymeric solid electrolyte are not in close contact with each other and the contact area between them is small. Thus, the battery shows low capacity and low energy density as compared to the amount of active material introduced thereto. If severe compression is carried out in order to increase the contact area between the active material particles and the polymeric solid electrolyte, the active material particles may be cracked to generate defects. Particularly, interfacial contact between the active material layer and the solid electrolyte membrane is insufficient when lithium ions of the electrode passes through the solid electrolyte membrane during charge/discharge, resulting in an increase in resistance, which ultimately adversely affects capacity realization and rate characteristics of the finished battery. For these reasons, in the case of an electrode using a solid electrolyte, it provides capacity lower than the designed or theoretical capacity, as compared to a battery using a liquid electrolyte.

DISCLOSURE Technical Problem

The present disclosure is designed to solve the problems of the related art, and therefore the present disclosure is directed to providing an all solid-state battery which has improved capacity realized by electrodes and enhanced output characteristics by increasing the contact area between electrode active material particles and a polymeric solid electrolyte to improve lithium ion conductivity. The present disclosure is also directed to providing a method for manufacturing the above-mentioned all solid-state battery.

Technical Solution

The present disclosure relates to an all solid-state battery and a method for manufacturing the same. According to the first embodiment of the present disclosure, there is provided an all solid-state battery which comprises a positive electrode, a negative electrode and a solid electrolyte membrane interposed between the positive electrode and the negative electrode, wherein at least one of the positive electrode, negative electrode or the solid electrolyte membrane comprises a polymeric solid electrolyte, the polymeric solid electrolyte comprises a swellable polymer electrolyte, either or both of the positive electrode and the negative electrode comprise an electrode active material layer comprising a plurality of electrode active material particles, a polymeric solid electrolyte and a conductive material, the gaps between the electrode active material particles in the electrode active material layer are filled with the polymeric solid electrolyte, the electrode active material layer comprises 1-100 parts by weight of the polymeric solid electrolyte based on 100 parts by weight of the electrode active material, and the positive electrode or the negative electrode independently has a porosity of 0-18%.

According to the second embodiment of the present disclosure, there is provided the all solid-state battery as defined in the first embodiment, wherein the polymeric solid electrolyte undergoes volumetric swelling by the infiltration of a vaporized organic solvent.

According to the third embodiment of the present disclosure, there is provided the all solid-state battery as defined in the first or the second embodiment, which is obtained through a solvent annealing process, wherein the porosity of the electrode active material layer is reduced by the solvent annealing and the difference in porosity between before and after the solvent annealing process is 0.5% or more.

According to the fourth embodiment of the present disclosure, there is provided the all solid-state battery as defined in any one of the first to the third embodiments, wherein the porosity is reduced by the swelling of the polymeric solid electrolyte after the solvent annealing process.

According to the fifth embodiment of the present disclosure, there is provided the all solid-state battery as defined in any one of the first to the fourth embodiments, wherein the polymeric solid electrolyte is a solid polymer electrolyte formed by adding a polymer resin to a solvated lithium salt.

According to the sixth embodiment of the present disclosure, there is provided a method for manufacturing an all solid-state battery, comprising the steps of: preparing a positive electrode, a negative electrode and a solid electrolyte membrane; interposing the solid electrolyte membrane between the positive electrode and the negative electrode to provide an electrode assembly; and subjecting the electrode assembly to a solvent annealing process to obtain an electrode, wherein at least one of the positive electrode, negative electrode or the solid electrolyte membrane comprises a polymeric solid electrolyte comprising a swellable polymer electrolyte.

According to the seventh embodiment of the present disclosure, there is provided the method for manufacturing an all solid-state battery as defined the sixth embodiment, wherein the polymeric solid electrolyte is a solid polymer electrolyte formed by adding a polymer resin to a solvated lithium salt.

According to the eighth embodiment of the present disclosure, there is provided the method for manufacturing an all solid-state battery as defined in the sixth or the seventh embodiment, wherein the solvent annealing process comprises the steps of: introducing the electrode assembly to a sealed space; filling the sealed space with a vaporized solvent; and allowing the electrode assembly to stand in the sealed space filled with the vaporized solvent.

According to the ninth embodiment of the present disclosure, there is provided the method for manufacturing an all solid-state battery as defined in eighth embodiment, wherein the solvent annealing process is carried out for 1-72 hours.

According to the tenth embodiment of the present disclosure, there is provided the method for manufacturing an all solid-state battery as defined in any one of the eighth to the ninth embodiments, wherein the solvent is at least one of an aprotic solvent selected from N,N-dimethyl acetamide (DMAc), N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), tetrahydrofuran (THF), acetonitrile, benzene, butyl acetate, chloroform, cyclohexane, 1,2-dichloroethane, ethyl acetate, diethyl ether, hexane, heptane, pentane, xylene or toluene; or a protic solvent selected from water, methanol, ethanol, propanol, n-butanol, isopropyl alcohol, decalin, acetic acid or glycerol.

According to the eleventh embodiment of the present disclosure, there is provided the method for manufacturing an all solid-state battery as defined in any one of the sixth to the tenth embodiments, wherein the polymeric solid electrolyte undergoes volumetric swelling by the infiltration of the vaporized organic solvent.

According to the twelfth embodiment of the present disclosure, there is provided the method for manufacturing an all solid-state battery as defined in any one of the eighth to the eleventh embodiments, wherein the vaporized solvent has a temperature of 15-200° C.

Advantageous Effects

In the electrode used in the all solid-state battery according to the present disclosure, the contact area between the electrode active material particles and the polymeric solid electrolyte is increased to provide increased reaction sites of the electrode active material. In addition, since the conductive material is distributed in such a manner that it is positioned more closely to the periphery of the active material, the contact frequency between the conductive material and the electrode active material particles is increased.

Further, in the all solid-state battery according to the present disclosure, the contact area between the electrode active material layer and the solid electrolyte membrane is increased to reduce resistance generated when lithium ions pass through the solid electrolyte membrane. Therefore, lithium ion transportability is increased during charge/discharge to improve capacity realized by the electrode.

DESCRIPTION OF DRAWINGS

The accompanying drawings illustrate a preferred embodiment of the present disclosure and together with the foregoing disclosure, serve to provide further understanding of the technical features of the present disclosure, and thus, the present disclosure is not construed as being limited to the drawing. Meanwhile, shapes, sizes, scales or proportions of some constitutional elements in the drawings may be exaggerated for the purpose of clearer description.

FIG. 1 is a schematic view illustrating an all solid-state battery which comprises an electrode comprising active material particles, a polymeric solid electrolyte and a conductive material according to the related art.

FIG. 2 is a schematic view illustrating an all solid-state battery which comprises an electrode comprising active material particles, a polymeric solid electrolyte and a conductive material according to an embodiment of the present disclosure.

BEST MODE

Hereinafter, preferred embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. Prior to the description, it should be understood that the terms used in the specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present disclosure on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Therefore, the description proposed herein is just a preferable example for the purpose of illustrations only, not intended to limit the scope of the disclosure, so it should be understood that other equivalents and modifications could be made thereto without departing from the scope of the disclosure.

Throughout the specification, the expression ‘a part ┌comprises┘ an element’ does not preclude the presence of any additional elements but means that the part may further include the other elements.

As used herein, the terms ‘approximately’, ‘substantially’, or the like, are used as meaning contiguous from or to the stated numerical value, when an acceptable preparation and material error unique to the stated meaning is suggested, and are used for the purpose of preventing an unconscientious invader from unduly using the stated disclosure including an accurate or absolute numerical value provided to help understanding of the present disclosure.

As used herein, the expression ‘A and/or B’ means ‘A, B or both of them’.

The present disclosure relates to a method for manufacturing an all solid-state battery and an all solid-state battery obtained thereby. According to the present disclosure, the all solid-state battery comprises a positive electrode, a negative electrode and a solid electrolyte membrane interposed between the positive electrode and the negative electrode. At least one of the positive electrode, negative electrode or the solid electrolyte membrane comprises a solid electrolyte, wherein the solid electrolyte may comprise at least one of a polymeric solid electrolyte or an inorganic solid electrolyte, and at least one of the positive electrode, negative electrode or the solid electrolyte membrane comprises a polymeric solid electrolyte.

FIG. 2 illustrates the all solid-state battery according to an embodiment of the present disclosure. Hereinafter, the all solid state battery according to the present disclosure will be explained in detail with reference to FIG. 2. The all solid-state battery 200 according to the present disclosure comprises two electrodes having opposite polarities and a solid electrolyte membrane 220 interposed between both electrodes. In addition, each electrode comprises an electrode active material layer 230, 240 formed on at least one surface of a current collector 211, 212.

According to an embodiment of the present disclosure, the electrode comprises a current collector and an electrode active material layer formed on at least one surface of the current collector, wherein the electrode active material layer comprises a plurality of electrode active material particles 231, a solid electrolyte 233 and a conductive material 232, wherein the solid electrolyte 233 comprises a polymeric solid electrolyte. Herein, the gaps between the electrode active material particles 231 are filled with the polymeric solid electrolyte 233 so that lithium ion transportability may be increased, and the conductive material 232 is positioned in the gaps between the electrode active material particles so that electrical conductivity may be increased.

In other words, according to an embodiment of the present disclosure, the electrode active material particles in the electrode active material layer are integrated with one another through dot-to-dot and/or face-to-face binding mainly by means of the polymeric solid electrolyte. In addition, the conductive material is dispersed in the polymeric solid electrolyte. According to an embodiment of the present disclosure, the polymeric solid electrolyte may comprise a swellable polymer electrolyte. For example, the polymeric solid electrolyte may comprise a swellable polymer electrolyte in an amount of 50 vol % or more, 70 vol % or more, 80 vol % or more, 90 vol % or more, or 95 vol % or more. Otherwise, the polymeric solid electrolyte may totally comprise a swellable polymer electrolyte. As used herein, the swellable polymer electrolyte refers to one that comprises a polymer material and undergoes volumetric swelling by the infiltration of an organic solvent. Therefore, the polymeric solid electrolyte in the electrode according to the present disclosure may be in an expanded (swelled) state at a predetermined ratio by solvent infiltration. Therefore, the gaps between active material particles are filled with the swelled polymer (polymer electrolyte), and thus the porosity of the electrode active material layer is decreased and the contact area between the polymer electrolyte and the active material particles is increased in the electrode active material layer, thereby providing effects of improving the characteristics of a battery, comprising effects of reducing resistance and increasing capacity.

To accomplish such effects, it is preferred that the polymeric solid electrolyte according to the present disclosure can be swelled by solvent annealing. In addition, the polymeric solid electrolyte covers the surface of electrode active material particles and/or fills the gaps between the electrode active material particles, and may be one having a broad electric potential window. For example, in the case of a positive electrode, the polymeric solid electrolyte may be one having high oxidation stability. In addition, in the case of a negative electrode, the polymeric solid electrolyte may be one having high reduction stability. For example, in terms of oxidation stability, the polymeric solid electrolyte may comprise a polycarbonate-based polymer electrolyte, polysiloxane-based polymer electrolyte, phosphazene-based polymer electrolyte, or the like. In terms of reduction stability, the polymeric solid electrolyte may comprise a polyether-based polymer electrolyte.

According to an embodiment of the present disclosure, the polymeric solid electrolyte may be swelled at a ratio larger than 1% to 1,000% through the solvent annealing process. Within the above-defined range, the swelling ratio may be 50% or more, 100% or more, 200% or more, 300% or more, 400% or more, 500% or more, 600% or more, 700% or more, or 800% or more. When the polymeric solid electrolyte has a swelling degree lower than the above-defined range, it is not possible to improve the interfacial contact between the active material and the electrolyte sufficiently. When the polymeric solid electrolyte is swelled at a ratio excessively higher than the above-defined ratio, the electrode has an excessively large thickness to cause degradation of energy density. The swelling degree of the polymeric solid electrolyte may be affected by the molecular weight and/or crosslinking degree of the polymer material. The polymeric solid electrolyte is swelled more, when it has a smaller molecular weight and has a lower or no crosslinking degree.

In general, ‘swelling’ means a phenomenon in which a material absorbs a solvent and its volume is expanded. As used herein, ‘swelling degree’ is obtained by measuring the volume of a polymeric solid electrolyte before (the initial volume) and after solvent annealing and calculating a volumetric increment therefrom, and may be expressed by the following Formula 1). For example, when a polymeric solid electrolyte has a swelling degree of 100%, it can be said that the electrolyte volume is doubled as compared to the volume before solvent annealing.

According to the present disclosure, the solvent annealing means that a polymeric solid electrolyte is exposed to a vaporized organic solvent for a predetermined time so that the vaporized organic solvent may infiltrate into the electrolyte. The exposure is carried out in a sealed space saturated with the steam of organic solvent, the exposure time may be controlled to 1-72 hours, and the temperature may be controlled to 15-200° C. According to an embodiment of the present disclosure, the temperature may be 30° C. or more, 50° C. or more, 70° C. or more, 90° C. or more, 110° C. or more, 130° C. or more, or 150° C. or more, and 140° C. or less, 130° C. or less, 120° C. or less, 100° C. or less, or 80° C. or less, within the above-defined range. In other words, the vaporized organic solvent may have a temperature ranging from 15-200° C.

Swelling degree (%)={(Volume of polymeric solid electrolyte after solvent annealing−Initial volume of polymeric solid electrolyte)/Initial volume of polymeric solid electrolyte}×100   Formula 1)

For example, the polymeric solid electrolyte may be one having the above-defined range of swelling degree according to Formula 1), when it is exposed to saturated N-methyl pyrrolidone (NMP) steam atmosphere at a temperature of 30° C. for 24 hours. Otherwise, Formula 1) may also be used to set solvent annealing conditions (solvent, temperature and/or exposure time) capable of providing the above-defined range of swelling degree to a selected polymer solid electrolyte.

As described hereinafter, the electrode for an all solid-state battery according to the present disclosure is obtained through a solvent annealing process during the manufacture thereof. Herein, the polymeric solid electrolyte is swelled by the infiltration of a vaporized solvent. Thus, the finished electrode has porosity lower than the porosity of the preliminary electrode. According to an embodiment of the present disclosure, the difference in porosity between the finished electrode for an all solid-state battery and the preliminary electrode may be 0.5% or more, 1% or more, 5% or more, or 10% or more. In addition, the electrode assembly of the all solid-state battery finished after the swelling may have a larger height as compared to the electrode assembly before the solvent annealing.

According to an embodiment of the present disclosure, the polymeric solid electrolyte mainly functions to transport lithium ions in the electrode and may be one having a desired ion conductivity, such as 10⁻⁷ S/cm or 10⁻⁴ S/cm or more. According to an embodiment of the present disclosure, one or more polymeric solid electrolytes may be used suitably in order to supplement electrode characteristics and to realize characteristics of electrode active material particles.

According to an embodiment of the present disclosure, the ion conductivity may be determined by measuring the electrochemical impedance of an electrolyte material by using a tester, such as VMP3 (Bio logic science instrument) and applying the nyquist plot assessment to the measured result.

According to the present disclosure, the polymeric solid electrolyte may be a polymer electrolyte formed by adding a polymer resin to a solvated lithium salt.

For example, the polymer electrolyte may comprise any one selected from the group consisting of a polyether polymer, polycarbonate polymer, acrylate polymer, polysiloxane polymer, phosphazene polymer, polyethylene derivatives, alkylene oxide derivatives, phosphate polymer, polyagitation lysine, polyester sulfide, polyvinyl alcohol, polyvinylidene fluoride and polymer containing an ionically dissociable group, or a mixture of two or more of them. However, the scope of the present disclosure is not limited thereto.

According to an embodiment of the present disclosure, the polymer electrolyte may comprise a polymer resin selected from the group consisting of a polymer resin, such as a branched copolymer comprising polyethylene oxide (PEO) backbone copolymerized with a comonomer comprising an amorphous polymer, such as PMMA, polycarbonate, polydiloxane (pdms) and/or phosphazene, comb-like polymer and crosslinked polymer resin, or a mixture of two or more of them.

In the electrolyte according to the present disclosure, the lithium salt is an ionizable lithium salt and may be represented by Li⁺X⁻. The anion (X⁻) of the lithium salt is not particularly limited, but may comprise F⁻, Cl⁻, BP, I⁻, NO₃ ⁻, N(CN)₂ ⁻, BF₄ ⁻, ClO₄ ⁻, PF₆ ⁻, (CF₃)₂PF₄ ⁻, (CF₃)₃PF₃, (CF₃)₄PF₂, (CF₃)₅PF⁻, (CF₃)₆P⁻, CF₃SO₃ ⁻, CF₃CF₂SO₃, (CF₃SO₂)₂N⁻, (FSO₂)₂N⁻, CF₃CF₂(CF₃)₂CO⁻, (CF₃SO₂)₂CH⁻, (SF₅)₃C⁻, (CF₃SO₂)₃C⁻, CF₃(CF₂)₇SO₃ ⁻, CF₃CO₂ ⁻, CH₃CO₂ ⁻, SCN⁻, (CF₃CF₂SO₂)₂N⁻, or the like.

According to an embodiment of the present disclosure, the electrode active material layer may comprise 1-100 parts by weight of the polymeric solid electrolyte based on 100 parts by weight of the electrode active material particles. Within the above-defined range, the polymeric solid electrolyte may be used in an amount of 2 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, or 70 parts by weight or more, and 95 parts by weight or less, 90 parts by weight or less, 80 parts by weight or less, 70 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, or 30 parts by weight or less. When the polymeric solid electrolyte is used in an amount larger than the upper limit, the proportion of the active material in the electrode is low to cause degradation of energy density. On the other hand, when the polymeric solid electrolyte is used in an amount smaller than the lower limit, the ion conductivity in the electrode is reduced to cause a decrease in capacity realization.

According to the present disclosure, the conductive material is not particularly limited, as long as it causes no chemical change in the corresponding battery and has conductivity. For example, the conductive material comprise any one selected from: graphite, such as natural graphite or artificial graphite; carbon black, such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black or thermal black; conductive fibers, such as carbon fibers (e.g. vapor grown carbon fibers (VGCF)) or metallic fibers; metal powder, such as carbon fluoride, aluminum or nickel powder; conductive whisker, such as zinc oxide or potassium titanate; conductive metal oxide, such as titanium oxide; and conductive materials, such as polyphenylene derivatives, or a mixture of two or more of them.

According to an embodiment of the present disclosure, the electrode active material layer may comprise the conductive material in an amount of 0-30 wt % based on 100 wt % of the electrode active material layer. According to an embodiment, the conductive material may be used in an amount of 0.5 wt % or more, 1 wt % or more, 3 wt % or more, or 5 wt % or more, and 15 wt % or less, 10 wt % or less, 7 wt % or less, or 5 wt % or less, within the above-defined range. For example, the conductive material may be used in an amount of 0.5-5 wt % based on 100 wt % of the electrode active material layer. When the amount of conductive material is larger than the upper limit, the proportion of active material is reduced to cause a decrease in energy density. When the amount of conductive material is smaller than the lower limit, it is not possible to realize a desired level of electron conductivity, resulting in degradation of capacity realization.

According to an embodiment of the present disclosure, the electrode may be any one of a negative electrode and a positive electrode. When the electrode is a negative electrode, the negative electrode active material may be any material used conventionally as a negative electrode active material for a lithium secondary battery. For example, the negative electrode active material may comprise at least one selected from: carbon such as non-graphitizable carbon, graphitic carbon, or the like; metal composite oxides such as Li_(x)Fe₂O₃ (0≤x≤1), Li_(x)WO₂(0≤x≤1), Sn_(x)Me_(1−x)Me′_(y)O_(z) (Me: Mn, Fe, Pb or Ge; Me′: Al, B, P, Si, an element of Group 1, Group 2 or Group 3 in the Periodic Table, or halogen; 0≤x≤1; 1≤y≤3; 1≤z≤8); lithium metal; lithium alloys; silicon-based alloys; tin-based alloys; metal oxides such as SnO, SnO₂, PbO, PbO₃, Pb₃O₃, Pb₃O₄, Sb₂O₃, Sb₂O₄, Sb₂O₅, GeO, GeO₂, Bi₂O₃, Bi₂O₄, Bi₂O₅, or the like; conductive polymers such as polyacetylene; Li—Co—Ni based materials; titanium oxide; and lithium titanium oxide, or the like. According to an embodiment of the present disclosure, the negative electrode active material may comprise a carbonaceous material and/or Si.

When the electrode is a positive electrode, the positive electrode active material may be any material used conventionally as a positive electrode active material for a lithium secondary battery. Non-limiting examples of the positive electrode active material may comprise, but are not limited to: layered compounds such as lithium cobalt oxide (LiCoO₂) and lithium nickel oxide (LiNiO₂), or those compounds substituted with one or more transition metals (Li_(1+a)[Ni_(x)Mn_(y)Co_((1−x−y))]M_(z)O₂, wherein 0≤a≤0.2, 0.4≤x≤0.9, 0<x+y<1, M is at least one element selected from the group consisting of Co, Mn, Ni, Al, Fe, V, Cr, Ti, Ta, Mg, Mo, Zr, W, Sn, Hf, Nd and Gd, and 0≤z≤0.1); lithium manganese oxides such as those represented by the chemical formula of Li_(1+x)Mn_(2−x)O₄ (wherein x is 0-0.33), LiMnO₃, LiMn₂O₃and LiMnO₂; lithium copper oxide (Li₂CuO₂); vanadium oxides such as LiV₃O₈, LiV₃O₄, V₂O₅ or Cu₂V₂O₇; Ni-site type lithium nickel oxides represented by the chemical formula of LiNi_(1−x)M_(x)O₂ (wherein M is Co, Mn, Al, Cu, Fe, Mg, B or Ga, and x is 0.01-0.3); lithium manganese composite oxides represented by the chemical formula of LiMn_(1−x)M_(x)O₂ (wherein M=Co, Ni, Fe, Cr, Zn or Ta, and x=0.01-0.1) or Li₂Mn₃MO₈ (wherein M=Fe, Co, Ni, Cu or Zn); lithium manganese composite oxides having a spinel structure and represented by the formula of LiNi_(x)Mn₂O_(2−x)O₄; LiMn₂O₄ in which Li is partially substituted with an alkaline earth metal ion; disulfide compounds; Fe₂(MoO₄)₃; or the like.

According to an embodiment of the present disclosure, the positive electrode active material and/or negative electrode active material may have a particle diameter of about 0.01-50 μm, and may have a shape of secondary particles formed by aggregation of a plurality of particles.

The electrode active material layer may be formed on at least one surface of a current collector. In addition, the electrode may further comprise a binder resin, if necessary.

According to the present disclosure, the binder resin is not particularly limited, as long as it is an ingredient which assists binding between the electrode active material and the conductive material and binding to the current collector. Particular examples of the binder resin comprise polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butyrene rubber, fluororubber, various copolymers, or the like. In general, the binder resin is added in an amount of 1-30 wt %, or 1-10 wt %, based on 100 wt % of electrode active material layer.

According to an embodiment of the present disclosure, the electrode may further comprise various additives in order to supplement or improve the physicochemical properties thereof. Although there is no particular limitation, the additives may comprise at least one of a flame retardant, heat stabilizer, anti-fogging agent, or the like.

According to the present disclosure, the current collector comprises a metal plate having electrical conductivity and may be one selected suitably depending on polarity of electrodes known in the field of secondary batteries. In addition, the current collector may have a thickness controlled adequately within a range of 1-50 μm.

According to an embodiment of the present disclosure, the finished electrode (electrode active material layer) may have a porosity selected adequately within a range of 0-20%. According to an embodiment of the present disclosure, the porosity may be 1% or more, 5% or more, 7% or more, 10% or more, or 15% or more, and 18% or less, 15% or less, 10% or less, or 7% or less. For example, the porosity may be 1-18% or 5-20%.

Since an all solid-state battery uses an electrolyte in a solid phase rather than a liquid phase, the contact area between the electrode active material and the solid electrolyte material is increased and the electrode active material is in closer contact with the solid electrolyte material, as the porosity is decreased, thereby realizing a desired level of ion conductivity. According to an embodiment of the present disclosure, the electrode for an all solid-state battery preferably has low porosity sufficient to realize a desired level of ion conductivity.

The term ‘porosity’ means a ratio of volume occupied by pores based on the total volume of a given structure, is expressed in the unit of %, and may be used interchangeably with the term of pore ratio or porous degree. According to the present disclosure, the porosity may be determined by any method with no particular limitation. For example, the porosity may be determined by using the Brunauer-Emmett-Teller (BET) method or Hg intrusion porosimetry. According to an embodiment of the present disclosure, the net density of an electrode active material layer is calculated from the density (apparent density) of a finished electrode (electrode active material layer) and the compositional ratio of ingredients contained in the electrode (electrode active material layer) and density of each ingredient. Then, the porosity of an electrode active material layer may be calculated from the difference between the apparent density and the net density.

According to the present disclosure, the solid electrolyte membrane is interposed between the negative electrode and the positive electrode, and functions as a selective barrier which allows lithium ion to pass therethrough while electrically insulating the negative electrode and the positive electrode from each other. The solid electrolyte membrane may comprise at least one of a polymeric solid electrolyte or an inorganic solid electrolyte. According to an embodiment of the present disclosure, the solid electrolyte membrane may comprise a polymeric solid electrolyte. Since the ingredients forming the solid electrolyte membrane are preferably swelled by solvent annealing to increase the interfacial contact between the solid electrolyte membrane and the electrode active material layer, it is preferred to use a polymeric solid electrolyte comprising a swellable polymer material having the above-described characteristics. In other words, according to an embodiment of the present disclosure, the solid electrolyte membrane may be in a state swelled by solvent infiltration to the polymeric solvent electrolyte. According to the present disclosure, the polymeric solid electrolyte contained in the solid electrolyte membrane is the same as the polymeric solid electrolyte contained in the above-described electrode, and thus description of the polymeric solid electrolyte will be omitted to avoid repetition.

However, the solid electrolyte membrane may be any solid electrolyte membrane used conventionally in the field of all solid-state batteries with no particular limitation. For example, the solid electrolyte membrane may comprise a mixture of a polymeric material with a lithium salt, wherein the polymeric material is any one selected from the group consisting of a polyethylene derivative, polyethylene oxide derivative, polypropylene oxide derivative, phosphate polymer, polyagitation lysine, polyester sulfide, polyvinyl alcohol and polyvinylidene fluoride, or a mixture of two or more of them. Herein, such materials may be used alone or in combination. In addition to the polymeric solid electrolyte ingredients, an inorganic solid electrolyte ingredient may be used optionally.

According to an embodiment of the present disclosure, the solid electrolyte membrane may have a thickness of about 10-100 μm. In addition, the solid electrolyte membrane preferably has an ion conductivity of 10⁻⁷ S/cm or more, or 10⁻⁴ S/cm or more.

Meanwhile, according to the present disclosure, the solid electrolyte membrane may further comprise at least one selected from sulfide-based solid electrolyte ingredients or oxide-based solid electrolyte ingredients.

In another aspect of the present disclosure, there are provided a battery module comprising the secondary battery as a unit cell, a battery pack comprising the battery module, and a device comprising the battery pack as a power source.

Herein, particular examples of the device may comprise, but are not limited to: power tools driven by an electric motor; electric cars, comprising electric vehicles (EV), hybrid electric vehicles (HEV), plug-in hybrid electric vehicles (PHEV), or the like; electric carts, comprising electric bikes (E-bikes) and electric scooters (E-scooters); electric golf carts; electric power storage systems; or the like.

Hereinafter, the method for manufacturing the above-described all solid-state battery will be explained. The following method is one of the embodiments that may be applied to manufacture the all solid-state according to the present disclosure and the scope of the present disclosure is not limited thereto.

First, a positive electrode, negative electrode and a solid electrolyte membrane for an all solid-state battery are prepared (S1). Herein, at least one of the negative electrode, positive electrode or the solid electrolyte membrane may comprise a polymeric solid electrolyte comprising a swellable polymer electrolyte.

Each of the electrodes may be prepared by the following method.

First, slurry for forming an electrode active material layer which comprises a polymeric solid electrolyte is prepared. Herein, the slurry may comprise a positive electrode active material or negative electrode active material depending on polarity.

Particularly, a mixture containing a polymeric solid electrolyte and a conductive material is prepared. The polymeric solid electrolyte may be provided in the form of a melt blend obtained by melting a polymer resin and lithium salt at high temperature or in the form of a solution containing a polymer resin and lithium salt dispersed homogeneously in an organic solvent. Then, the conductive material is added to the blend or solution, followed by mixing, to provide a mixture. The mixture may further comprise a binder resin, if necessary. In addition, electrode active material particles are added thereto and mixed to prepare slurry for forming an electrode active material layer. The content of each of the electrode active material, polymeric solid electrolyte and the conductive material in the slurry may be the same as described above.

However, the above-mentioned method for preparing slurry is an exemplary embodiment and the scope of the present disclosure is not limited thereto. Particularly, the order of introduction or mixing of slurry ingredients may be modified considering the physicochemical properties of ingredients and the characteristics of an electrode or battery to be obtained. For example, the polymeric solid electrolyte, conductive material and the electrode active material may be introduced to a dispersion medium, such as a solvent, at different times or at the same time.

Next, the slurry is coated on at least one of a current collector to obtain an electrode (S2). The electrode obtained from this step is an electrode not subjected to solvent annealing.

The coating may be carried out by applying the slurry onto at least one surface of a current collector, followed by drying, and performing compression, if necessary. The slurry may be applied by using a conventional slurry coating process, such as doctor blade coating or slot die coating. Then, the applied slurry is dried and subjected to a compression process, if necessary. The compression process allows packing of ingredients so that the electrode active material layer may have an adequate level of porosity and is not limited to a particular method. For example, any known compression method, such as hot pressing or rolling, may be used suitably, and may be optionally controlled to a suitable temperature condition through heating or cooling.

Once the positive electrode and negative electrode are prepared by the above-described method, a solid electrolyte membrane is interposed between the positive electrode and the negative electrode to provide an electrode assembly (S2). The electrode assembly may be assembled by using a method currently used in the art. For example, a lamination process may be carried out by stacking the positive electrode, solid electrolyte membrane and the negative electrode successively to prepare a stack, and applying a predetermined level of pressure to the stack. In addition, a binder layer may be further interposed in the positive electrode, solid electrolyte member and the negative electrode in order to increase interlayer adhesion. Meanwhile, according to an embodiment of the present disclosure, the solid electrolyte membrane may be obtained by preparing a melt blend through hot melting of a polymeric resin and a lithium salt or a solution containing a polymeric resin and a lithium salt dispersed homogeneously therein, and forming the melt blend or solution into a film shape. In a variant, the blend or solution may be coated on the electrode surface to provide a structure comprising the electrodes integrated with the electrolyte membrane. The polymer resin is not particularly limited, as long as it is used conventionally for preparing a solid electrolyte in the art, and the electrolyte member may comprise a polymeric solid electrolyte comprising a swellable polymer electrolyte.

After that, the resultant electrode assembly is subjected to a solvent annealing process (S3). Through the solvent annealing, the polymeric solid electrolyte is exposed to a vaporized organic solvent and the vaporized organic solvent infiltrates into the solid electrolyte to cause volumetric swelling of the electrolyte. The solvent annealing process may comprise the steps of: introducing the electrode assembly to a sealed space (e.g. chamber); filling the sealed space with a vaporized solvent; and allowing the electrode assembly to stand in the sealed space filled with the vaporized solvent for a predetermined time.

In the step of allowing the electrode assembly to stand in the sealed space, the vaporized solvent infiltrates into the polymeric solid electrolyte, and thus the polymeric solid electrolyte is swelled. According to an embodiment of the present disclosure, the sealed space may be filled with the vaporized solvent by vaporizing the solvent in a separate space linked to the chamber through a pipe and injecting the vaporized solvent to the chamber. In a variant, a liquid solvent is received in a separately prepared container, the container is introduced to a chamber, and the chamber is heated so that the solvent may be vaporized directly in the chamber. Herein, it is preferred that the liquid solvent is spaced apart from the electrode assembly by a predetermined interval so that they may not be in direct contact with each other.

Meanwhile, it is possible to change the order of the step of introducing the electrode assembly to a sealed space (e.g. chamber) and the step of filling the sealed space with the vaporized solvent, if necessary.

For example, the chamber may be filled with the vaporized solvent before the electrode assembly is introduced to the chamber. According to an embodiment of the present disclosure, the vaporization step may be carried out at a temperature ranging from about 15-200° C., considering the vapor pressure or boiling point of the solvent. For example, the vaporization step may be carried out at room temperature of about 20-30° C. or may be carried out at a higher temperature, such as about 200° C. or lower, through heating. In other words, according to an embodiment of the present disclosure, the vaporized solvent may have a temperature of about 15-200° C., and solvent annealing may be carried out in the chamber filled with the vaporized solvent at the above-defined range of temperature for a predetermined time.

According to an embodiment of the present disclosure, the sealed space, such as a chamber, in which solvent annealing is carried out should be saturated with the vaporized solvent. To accomplish this, the sealed space is maintained at least under the vapor pressure of the solvent. According to an embodiment of the present disclosure, the vaporized solvent may be introduced continuously until the solvent annealing is terminated. Otherwise, when the liquid solvent is also introduced to the chamber and heated, an excessive amount of solvent is introduced so that the solvent may not be totally vaporized but a residual amount of solvent may remain until the solvent annealing process is terminated. The amount of solvent may be determined considering the amount (volume or weight) of the polymeric solid electrolyte used for the electrode assembly and/or chamber size. For example, when using N-methyl pyrrolidone (NMP) is used as a solvent, the chamber may have a size of about 300 mL. In addition, when solvent annealing is carried out at 130° C. for 24 hours, about 300 μL of NMP may be introduced.

According to an embodiment of the present disclosure, the solvent used for solvent annealing is not particularly limited, as long as it is chemically stable and particularly it causes no deterioration of an electrode when being applied to the battery. For example, it is possible to use a solvent selected from solvents that may be used as electrolytes for electrochemical devices. For example, the solvent may comprise at least one selected from cyclic, linear or branched carbonates, linear esters, ethers, or the like. Non-limiting examples of such solvents may comprise propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl propionate (MP), dimethyl sulfoxide, dimethoxyethane, diethoxyethane, tetrahydrofuran, N-methyl-2-pyrrolidone (NMP), ethyl methyl carbonate (EMC), vinylene carbonate (VC), gamma-butyrolactone (GBL), fluoroethylene carbonate (FEC), methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, pentyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, or the like. In addition, the solvent may comprise at least one of an aprotic solvent selected from N,N-dimethyl acetamide (DMAc), N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), tetrahydrofuran (THF), acetonitrile, benzene, butyl acetate, chloroform, cyclohexane, 1,2-dichloroethane, ethyl acetate, diethyl ether, hexane, heptane, pentane, xylene or toluene; or a protic solvent selected from water, methanol, ethanol, propanol, n-butanol, isopropyl alcohol, decalin, acetic acid or glycerol.

In addition, solvent annealing may be carried out for 1-72 hours and the solvent annealing time may be controlled adequately. For example, the solvent annealing time may be 2 hours or more, 10 hours or more, 20 hours or more, 30 hours or more, or 50 hours or more, or 65 hours or less, 60 hours or less, 50 hours or less, 40 hours or less, or 30 hours or less, within the above-defined range. When the annealing time is within the above-defined ranges, solvent annealing may be carried out efficiently through solvent evaporation. In addition, when the annealing time is longer than the above-defined range, productivity is decreased due to an increase in electrode processing time. When the annealing time is shorter than the above-defined range, the polymeric solid electrolyte may not be swelled homogeneously.

Meanwhile, according to an embodiment of the present disclosure, a compression step may be further carried out in order to control the porosity, after completing the solvent annealing.

In the all solid-state battery obtained by the above-described method, the polymeric solid electrolyte contained in the electrode assembly is swelled homogeneously so that the active material particles, polymeric solid electrolyte and the conductive material may be bound to one another through face-to-face binding and dot-to-dot binding, and the electrolyte membrane forming the all solid-state battery is swelled uniformly to increase interfacial contact with the active material layer, thereby providing an effect of improving ion conductivity during charge/discharge.

FIG. 1 is a schematic view illustrating the all solid-state battery obtained by the conventional method. According to the conventional method, the electrode is obtained by mixing an electrode active material, polymeric solid electrolyte and a conductive material all at once to prepare electrode slurry, and coating the slurry onto a current collector. In this case, the electrode active material is not in close contact with the solid electrolyte and the contact area is small, and thus it is not possible to ensure sufficient electrochemical reaction sites between the electrode active material and the solid electrolyte. As a result, there are problems in that battery performance cannot be realized sufficiently due to a decrease in capacity, degradation of output characteristics, a decrease in ion conductivity, an increase in interfacial resistance, or the like.

To solve the above-mentioned problems, there is a need for a compression step in which the electrode surface is compressed under a high pressure condition, after coating the electrode or during the lamination process in forming the electrode assembly, in order to increase the contact area between the electrode active material and polymeric solid electrolyte. However, in this case, there are problems in that the electrode active material is cracked due to the high pressure applied during the compression step, resulting in degradation of battery capacity and life characteristics.

FIG. 2 is a schematic view illustrating the all solid-state battery 200 which comprises an electrode comprising an electrode active material layer 230, 240 on one surface of each current collector 211, 212 according to an embodiment of the present disclosure. Referring to FIG. 2, the polymeric solid electrolyte 233 in the electrode active material layer 230, 240 is swelled homogeneously as a whole by the solvent steam infiltrated during the solvent annealing process so that the conductive material 232 may be positioned near the surface of the electrode active material particles 231, and thus participate in electrochemical reactions at a higher ratio. As a result, the use of conductive material can be reduced. In addition, it is possible to ensure sufficient reaction sites even when no severe pressure is applied during the compression of the electrode, and thus to prevent deterioration of the electrode. Additionally, it is possible to increase lithium ion transportability and capacity realization of the active material. Further, the solid electrolyte membrane 220 is also swelled by the solvent steam infiltrated during the solvent annealing process so that the interfacial contact with the electrode active material layer 230, 240 may be increased. Thus, it is possible to reduce the resistance generated when electrode lithium ions pass through the solid electrolyte membrane during charge/discharge.

In addition, there are provided a battery module comprising the all solid-state battery as a unit cell, a battery pack comprising the battery module, and a device comprising the battery pack as a power source.

Herein, particular examples of the device may comprise, but are not limited to: power tools driven by an electric motor; electric cars, comprising electric vehicles (EV), hybrid electric vehicles (HEV), plug-in hybrid electric vehicles (PHEV), or the like; electric carts, comprising electric bikes (E-bikes) and electric scooters (E-scooters); electric golf carts; electric power storage systems; or the like.

Examples will be described more fully hereinafter so that the present disclosure can be understood with ease. However, the following examples are for illustrative purposes only and the scope of the present disclosure is not limited thereto.

EXAMPLES Manufacture of Electrode and Battery Example 1

(1) Manufacture of Electrode

First, NCM811 (LiNi_(0.8)Co_(0.1)Mn_(0.1)O₂) as an electrode active material, vapor grown carbon fibers (VGCF) as a conductive material, and a polymeric solid electrolyte (a mixture of polyethylene oxide (PEO) with LiFSI ((LiCF₃SO₂)₂N), molar ratio of PEO:LiFSI, [EO]:[Li⁺]=20:1) were mixed at a weight ratio of 80:3:17 and the resultant mixture was introduced to acetonitrile, followed by agitation, to provide electrode slurry. An aluminum current collector having a thickness of 20 μm was prepared. The slurry was applied to the current collector by using a doctor blade and the resultant product was vacuum-dried at 120° C. for 4 hours. Then, compression was carried out by using a roll press device to obtain an electrode having a loading amount of 2 mAh/cm², an electrode active material layer thickness of 48 μm and a porosity of 22%. The porosity means the ratio of volume of pores (pore volume) occupied by pores based on the total volume. The porosity was calculated by using the apparent density calculated from the volume and weight of each electrode active material layer and the net density calculated from the compositional ratio of the ingredients and density of each ingredient, as well as the pore volume obtained therefrom.

(2) Manufacture of Battery

The electrode obtained from (1) was cut into a circular shape with an area of 1.4875 cm², and lithium metal foil cut into a circular shape with an area of 1.7671 cm² was used as a counter electrode to obtain an electrode assembly. Particularly, a solid electrolyte membrane (a mixture of PEO with LiFSI ((LiCF₃SO₂)₂N), molar ratio of [EO]:[Li⁺]=20:1) having a thickness of 50 μm was interposed between the electrode and lithium metal.

(3) Solvent Annealing Process

Then, the electrode assembly was introduced to a chamber (300 mL) and 300 μL of N-methyl pyrrolidone (NMP) was introduced to the chamber together with the electrode assembly in such a manner that the solvent might not be in direct contact with the electrode. The chamber was sealed and was maintained at 60° C. for 24 hours to carry out solvent annealing. The porosity of the electrode active material layer was calculated according to the above-mentioned method, and the electrode active material layer of the finished electrode assembly had a porosity of 10%.

Example 2

A battery was obtained in the same manner as Example 1, except that solvent annealing was carried out at room temperature. Before solvent annealing, the electrode active material layer of the electrode assembly had a porosity of 22%. After solvent annealing, the electrode active material layer of the electrode assembly had a porosity of 16%.

Example 3

A battery was obtained in the same manner as Example 1, except that solvent annealing was carried out at room temperature for 2 days. Before solvent annealing, the electrode active material layer of the electrode assembly had a porosity of 22%. After solvent annealing, the electrode active material layer of the electrode assembly had a porosity of 13%.

Comparative Example 1

A battery was obtained in the same manner as Example 1, except that solvent annealing was not carried out. The electrode active material layer had a porosity of 22%.

Test Example 1 Evaluation of Initial Discharge Capacity and Output Characteristics

Each of the batteries according to Examples 1-3 and Comparative Example 1 was charged/discharged to evaluate the initial discharge capacity and capacity retention. Meanwhile, when evaluating output characteristics, the first charge/discharge were carried out at 60° C. and 0.05 C, the second charge/discharge were carried out at 0.2 C, the cycles were terminated in a discharged state, and output characteristics were evaluated.

Charge condition: CC (constant current)/CV (constant voltage), (4.0V, 0.005 C current cut-off)

Discharge condition: CC (constant current), 3V.

The capacity retention was derived by calculating the ratio of discharge capacity after 30 cycles based on discharge capacity at the first cycle. The results are shown in the following Table 1.

TABLE 1 Discharge capacity Output characteristics (mAh/g, 4.0 V) (%, 0.2 C/0.05 C, 4.0 V) Example 1 138 73 Example 2 134 70 Example 3 136 72 Comp. Ex. 1 126 61

As can be seen from the foregoing, addition of a solvent annealing process after the assemblage of a cell results in swelling of the solid electrolyte in the cell, increases the contact area between the electrode active material and the solid electrolyte, and improves the contact area between the solid electrolyte membrane and the electrode to facilitate intercalation/deintercalation of lithium ions. As a result, it can be seen that discharge capacity and output characteristics are improved by 10% or more. 

1. An all solid-state battery which comprises a positive electrode, a negative electrode and a solid electrolyte membrane interposed between the positive electrode and the negative electrode, wherein either or both of the positive electrode and the negative electrode comprise an electrode active material layer comprising a plurality of electrode active material particles, a polymeric solid electrolyte and a conductive material, the gaps between the electrode active material particles in the electrode active material layer are filled with the polymeric solid electrolyte, the polymeric solid electrolyte comprises a swellable polymer electrolyte, the polymeric solid electrolyte is in a swelled state by solvent infiltration, and the electrode active material layer has a porosity of 0-18%.
 2. The all solid-state battery according to claim 1, wherein the polymeric solid electrolyte in a swelled state is obtained through volumetric swelling by the solvent infiltration of a vaporized organic solvent.
 3. The all solid-state battery according to claim 1, wherein the polymeric solid electrolyte in a swelled state is obtained through a solvent annealing process, wherein the porosity of the electrode active material layer is reduced by the solvent annealing process and the difference in porosity between before and after the solvent annealing process is 0.5% or more.
 4. The all solid-state battery according to claim 3, wherein the porosity of the electrode active material layer is reduced by swelling of the polymeric solid electrolyte after the solvent annealing process.
 5. The all solid-state battery according to claim 1, wherein the polymeric solid electrolyte is a solid polymer electrolyte formed by adding a polymer resin to a solvated lithium salt.
 6. A method for manufacturing an all solid-state battery, comprising the steps of: preparing a positive electrode, a negative electrode and a solid electrolyte membrane; interposing the solid electrolyte membrane between the positive electrode and the negative electrode to provide an electrode assembly; and subjecting the electrode assembly to a solvent annealing process to obtain an electrode, wherein at least one of the positive electrode, negative electrode or the solid electrolyte membrane comprises a polymeric solid electrolyte comprising a swellable polymer electrolyte.
 7. The method for manufacturing an all solid-state battery according to claim 6, wherein the polymeric solid electrolyte is a solid polymer electrolyte formed by adding a polymer resin to a solvated lithium salt.
 8. The method for manufacturing an all solid-state battery according to claim 6, wherein the solvent annealing process comprises the steps of: introducing the electrode assembly to a sealed space; filling the sealed space with a vaporized solvent; and allowing the electrode assembly to stand in the sealed space filled with the vaporized solvent.
 9. The method for manufacturing an all solid-state battery according to claim 8, wherein the solvent annealing process is carried out for 1-72 hours.
 10. The method for manufacturing an all solid-state battery according to claim 8, wherein the solvent is at least one of an aprotic solvent selected from N,N-dimethyl acetamide (DMAc), N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) or N,N-dimethylformamide (DMF); or a protic solvent selected from water, methanol, ethanol, propanol, n-butanol, isopropyl alcohol, decalin, acetic acid or glycerol.
 11. The method for manufacturing an all solid-state battery according to claim 6, wherein the polymeric solid electrolyte undergoes volumetric swelling by the infiltration of a vaporized organic solvent in the solvent annealing process.
 12. The method for manufacturing an all solid-state battery according to claim 8, wherein the solvent annealing process is carried out at a temperature of 15-200° C.
 13. The all solid-state battery according to claim 1, wherein the solid electrolyte membrane comprises a second polymeric solid electrolyte, wherein the second polymeric solid electrolyte comprises a swellable polymer electrolyte, and the solid electrolyte membrane is in a swelled state by solvent infiltration.
 14. The all solid-state battery according to claim 1, wherein the swellable polymer electrolyte is included in an amount of 50 vol % or more in the polymeric solid electrolyte.
 15. The all solid-state battery according to claim 1, wherein the polymer solid electrolyte comprises a polycarbonate-based polymer electrolyte, a polysiloxane-based polymer electrolyte, a phosphazene-based polymer electrolyte, or a polyether-based polymer electrolyte.
 16. The all solid-state battery according to claim 1, wherein the polymer solid electrolyte comprises one selected from the group consisting of a polyether polymer, polycarbonate polymer, acrylate polymer, polysiloxane polymer, phosphazene polymer, polyethylene derivatives, alkylene oxide derivatives, phosphate polymer, polyagitation lysine, polyester sulfide, polyvinyl alcohol, polyvinylidene fluoride and polymer containing an ionically dissociable group, or a mixture thereof.
 17. The all solid-state battery according to claim 1, wherein the electrode active material layer comprises 1-100 parts by weight of the polymeric solid electrolyte based on 100 parts by weight of the electrode active material particles.
 18. The all solid-state battery according to claim 1, wherein the electrode active material layer comprises the conductive material in an amount of 0-30 wt % based on 100 wt % of the electrode active material layer.
 19. The all solid-state battery according to claim 1, wherein the solid electrolyte membrane has a thickness of about 10-100 μm.
 20. The method for manufacturing an all solid-state battery according to claim 6, wherein the polymeric solid electrolyte is swelled at a swelling degree of larger than 1% to 1,000% after the solvent annealing process. 